New water soluble diazo akino compounds



Patented July 12, 1932 UNITED STATES -PATENT OFFICE ANTON OSSENBEOK, OF OOIDGNE-I'O'LHEm-ON-TEE-RHINE, AND EH81 TIETZE, OI

GOLOGNE-ON-THE-BHINE, GERMANY, ASSIGNORS TO GENERAL ANILINE WORKS, INC, 01' NEW YORK, N. Y, A CORPORATION OI DELAWARE NEW WATER SOLUBLE DIAZO AMINO COMPOUNDS Io Drawing. Application filed January 20, 1880, Serial No. 422,814, and in Germany January 28, 1929.

The present invention relates to new water soluble diazo amino" compounds, more particularly to com'pounds of the probable general formula wherein R, R the Ys and n have the above indicated meaning.

The sulfamides of the general formula:

wherein R, R and n have the above indicated meaning, are obtainable by condensing an aromatic monoor di-amino-nitro compound with one or two molecules, respectively, of an aromatic sulfochloride and re ducing the nitro compound thus formed. The reactions involved may be illustrated by the general scheme:

om-n- Nm c1.so,.m).

o,Nn-[NH.s0,. 121] wherein R, R and n are identified as above. The sulfamides of the general formula:

iiN-n-[sommnd wherein R, R and n have the above signification, maybe prepared by condensing an aromatic nitro-monoor di-sulfochloride with one or two molecules, respectively, of an aromatic amine and reducing the nitro compound thus formed to the corresponding 'chloro-2-amino-l-methylbenzene,

I HzNQCH:

OaNH-O 4-methyl 1-aminobenzene-3-sulfamide:

HaNQ-OH:

OI-NHI 1-am-ino-2.4-di- [phenylsulfamino] -benzene mNQmasm-O Hem-O or such sulfamides of the benzene series in which the benzene nuclei are substituted by monovalent substituents, such as alkyl groups, nitro groups, alkoxygroups, halogen atoms, or the like, or also such sulfamides of the above general formula in which R or R stand for substituted or unsubstituted naphthalene nuclei.

Our new products are prepared, for example, by diazotizing in the usual manner an aromatic amine with sodium nitrite and hydrochloric acid, adding the diazo solution to a hydrochloric acid solution of the sulfamide and neutralizing the solution.

Any desired kind of diazotizable aromatic amines can be used for this process, for example 2.5 dichloro 1 amino benzene, 4 chloro 2 amino 1 methylbenzene, 4.5-di- 5-nitro-2- amino-l-methylbenzene, 3-chloro 1 aminobenzene, 4 chloro 2 amino-l-methoxybenzene, 4-nitro-2-amino-1-methoxybenzene, 3- amino-4-methoxy 6 -nitro 1 methylbenzene, 3-0.mino-4-methoxy-6-benzoylamino 1 methylbenzene, 6-amino-3-benzoylamino-4-ethoxy-l-methoxybenzene, aor ,B-naphthylamine or nuclear substitution products there-.

HzN OH:

QI H-O and the reaction to Congo red is gradually caused to disappear by the addition of sodium acetate or sodium carbonate. After a few hours the diazo compound is no longer detectable, and the diazoamino compound of the formula separates. The latter is dissolved in caustic soda lye and salted out with sodium chloride, whereupon the sodium salt first separates in the form of a resinous mass. After filtering and drying it forms a yellowish brown owder readily soluble in water, the solution eing readily split up again by acids into the initial components.

Example 2.-On replacing the 3-chloroaniline (in Example 1.) by the equivalent quantity of 2.5-dichloro-aniline there is obtained a product of the formula 2- possessing completely analogous properties.

Ea'ample- 3.140 parts by weight of 4-nitroaniline are diazotized in the customary manner with 69 parts by Weight of sodium nitrite in hydrochloric acid solution. The solution of the diazoniuln salt is then allowed to run into a hydrochloric acid solution of 4 amino-2- [phenylsulfamino] -1-methyl-benzene and worked up in the manner indicated in Example 1. The diazoamino compound of theformula:

is thus obtained in the form of a brownish powder, soluble in water.

Ea-ample 4.In a similar manner as described in the above examples there is formed the diazo amino compound from 2-methyl-4- nitro-l-benzene diazoniumchloride and 1- amino-2.4-di- [phenylsulfamino] -benzene of the formula:

H... ago

NILSOrobtainable by reacting with benzenesulfochloride upon 1-nitro-2.4 phenylendiamine and reduction. The product formed has the probable formula:

CHI O:NON=NNHQNHSOr-O We claim 1. As new products, the compounds of the probable formula aHHU O v wherein the benzene nuclei may be substituted by monovalent substituents of the group consisting of alkyl, alkoxy, nitro and halogen, said products forming yellowish to yellow brown compounds, rather diflicultly soluble in the usual organic solvents, solu ble in alkalies, and being easily split up by acids.

' 2. As a new product, the compound of the probable formula QaHHQOH. 1 OzNHO said product being in the form of its sodium salt a yellowish brown powder, readily soluble in water, and being split up by acids.

3; As new products, the compounds of the probable general formula:

wherein the Rs and R represent residues of the benzene-or naphthalene series, one Y means the group S0 and the other Y the group NH, and n stands for one of the numbers 1 or 2, said products forming yellowish to yellow-brown compounds, being rather difiicultly soluble in the usual organic solvents, soluble in alkalies, and being easily split up by acids.-

4. As new products, the compounds of the probable general formula: B-N=N-NH-n-!.r.n

wherein the Rs stand for residues of the benzene series, one Y represents the group S0 and the other Y the group NH, said products forming yellowish to yellow-brown compounds, being rather diflicultly soluble in the usual organic solvents, soluble in alkalies, and being easily split up by acids. 5. As a new product, the compound of the probable formula:

' tures.

zen-meQ-om 20 said product being in the form of its sodium salt a yellowish brown powder, readily soluble in water, and being split up by acids.

In testimony whereof, we afiix our signa- ANTON OSSENBECK. ERNST TIETZE. 

